Branched aromatic sulfide/sulfone polymer production

Abstract

A first reaction mixture of at least one dihalo aromatic sulfone, at least one polyhydroxy aromatic compound, at least one organic amide and at least one alkali metal carbonate is contacted under polymerization conditions including a period of time at a temperature sufficient to form a reaction product, with the resulting product mixture being contacted with at least one polymerizable sulfur source, at least one organic amide, at least one alkali metal carboxylate, and water under polymerization conditions including a period of time at a temperature sufficient to form a branched aromatic sulfide sulfone polymer. The resulting polymers are useful in the production of coatings, films, molded objects, and fibers.

We claim: 
     
       1. A process for producing branched polyarylene sulfide sulfone, said process comprising: (a) contacting at least one dihalo aromatic sulfone monomer with at least one polyhydroxy aromatic compound having at least three hydroxy groups, at least one organic amide and at least one alkali metal carbonate at a temperature and pressure and for a time sufficient to produce a first reaction product mixture;   (b) contacting a reaction mixture comprising: (1) said first reaction product mixture,   (2) at least one polymerizable sulfur source selected from the group consisting of alkali metal sulfides and alkali metal hydrosulfides,   (3) at least one organic amide,   (4) at least one alkali metal carboxylate, and   (5) water at a temperature and pressure and for a time sufficient to produce branched polyarylene sulfide sulfone, and       (c) recovering said branched polyarylene sulfide sulfone from said reaction mixture.   
     
     
       2. A process of claim 1 wherein said at least one dihalo aromatic compound is represented by the formula: ##STR3## where each X is selected from the group consisting of fluorine, chlorine, bromine and iodine; z is a divalent radical selected from the group consisting of: ##STR4## wherein m is 0 or 1; n is 0 or 1; A is selected from the group consisting of oxygen, sulfur, sulfonyl, and CR 2  ; and each R is selected from the group consisting of hydrogen and alkyl radicals having 1 to about 4 carbon atoms, the total number of carbon atoms in all of the R groups in the molecule being 0 to about 12. 
     
     
       3. A process of claim 2 wherein said at least one dihalo aromatic compound is chosen from the group consisting of bis(p-fluorophenyl) sulfone, bis(p-chlorophenyl) sulfone, bis(p-bromophenyl) sulfone, bis(p-iodophenyl) sulfone, p-chlorophenyl p-bromophenyl sulfone, p-iodophenyl 3-methyl-4-fluorophenyl sulfone, bis(2-methyl-4-chlorophenyl) sulfone, bis(2,5-diethyl-4-bromophenyl) sulfone, bis(3-isopropyl-4-iodophenyl) sulfone, bis(2,5-dipropyl-4-chlorophenyl) sulfone, bis(2-butyl-4-fluorophenyl) sulfone, bis(2,3,5,6-tetramethyl-4-chlorophenyl) sulfone, 2-isobutyl-4-chlorophenyl 3-butyl-4-bromophenyl sulfone, 1,4-bis(chlorophenyl-sulfonyl)benzene, 1-methyl-2,4-bis(p-fluorophenylsulfonyl)benzene, 2,6-bis(p-bromophenylsulfonyl)naphthalene, 7-ethyl-1,5-bis(p-iodophenylsulfonyl)naphthalene, 4,4'-bis(p-chloro-phenylsulfonyl)biphenyl, bis[p-(p-bromophenylsulfonyl)phenyl] ether, bis[p-(p-chlorophenylsulfonyl)phenyl] sulfide, bis[p-(p-chlorophenylsulfonyl)phenyl] sulfone, bis[p-(p-bromophenylsulfonyl)phenyl]methane, 5,5-bis[3-ethyl-4-chlorophenylsulfonyl)phenyl]nonane and mixtures thereof. 
     
     
       4. A process of claim 3 wherein said at least one dihalo aromatic compound is bis(p-chlorophenyl) sulfone. 
     
     
       5. A process of claim 1 wherein said at least one alkali metal carbonate is chosen from the group consisting of sodium carbonate, lithium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate and mixtures thereof. 
     
     
       6. A process of claim 5 wherein said at least one alkali metal carbonate is sodium carbonate. 
     
     
       7. A process of claim 1 wherein said at least one polyhydroxy aromatic compound is chosen from the group consisting of 1,2,3-trihydroxybenzene (pyrogallol), 1,2,4-trihydroxybenzene (hydroxyquinol), 1,3,5-hydroxybenzene (phloroglucinol) and tris(4-hydroxyphenyl)methane (leucoaurin). 
     
     
       8. A process of claim 7 wherein said at least one polyhydroxy aromatic compound is 1,3,5-hydroxybenzene (phloroglucinol). 
     
     
       9. A process of claim 1 wherein said at least one polymerizable sulfur source is chosen from the group consisting of sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, sodium hydrosulfide, lithium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and mixtures thereof. 
     
     
       10. A process of claim 9 wherein said at least one polymerizable sulfur source is sodium sulfide. 
     
     
       11. A process of claim 1 wherein said at least one organic amide is chosen from the group consisting of formamide, acetamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpropionamide, N,N-dipropylbutyramide, 2-pyrrolidone, N-methyl-2-pyrrolidone, -caprolactam, N-methyl- -caprolactam, N,N'-ethylenedi-2-pyrrolidone, hexamethylphosphoramide, tetramethylurea and mixtures thereof. 
     
     
       12. A process of claim 11 wherein said at least one organic amide is N-methyl-2-pyrrolidone. 
     
     
       13. A process of claim 1 wherein said at least one alkali metal carboxylate is represented by the formula R'CO 2  M, where R' is a hydrocarbyl radical selected from the group consisting of alkyl, cycloalkyl, and aryl and combinations thereof and the number of carbon atoms in R' is within the range of 1 to about 20 and M is an alkali metal. 
     
     
       14. A process of claim 13 wherein said at least one alkali metal carboxylate is chosen from the group consisting of alkali metal acetate, alkali metal propionate, alkali metal 2-methylpropionate, alkali metal butyrate, alkali metal valerate, alkali metal hexanoate, alkali metal heptanoate, alkali metal 2-methyloctanoate, alkali metal dodecanoate. alkali metal 4-ethyltetradecanoate, alkali metal octadecanoate, alkali metal heneicosanoate, alkali metal cyclohexanecarboxylate, alkali metal cyclododecanecarboxylate, alkali metal methylcyclopentane, carboxylate, alkali metal cyclohexylacetate, alkali metal benzoate, alkali metal m-toluate, alkali metal phenylacetate, alkali metal 4-phenylcyclohexanecarboxylate, alkali metal p-tolylacetate, alkali metal 4-ethylyclohexylacetate and the mixtures thereof and said alkali metal is chosen from the group consisting of sodium, lithium, potassium, rubidium and cesium. 
     
     
       15. A process of claim 14 wherein said at least one alkali metal carboxylate is sodium acetate. 
     
     
       16. A process of claim 1 wherein said contacting of (a) is at a pressure suitable to keep said dihalo aromatic sulfone monomer in solution, at a temperature in the range of about 150° C. to about 200° C. and a reaction time in a range of about 5 minutes to about 24 hours, and said contacting of (b) at a pressure suitable to keep said organic amide substantially in the liquid phase, at a temperature of about 170° C. to about 230° C. and for a time in a range of about 5 minutes to about 3 days.   
     
     
       17. A process of claim 16 wherein said contacting of (a) takes place at a pressure suitable to keep said organic amide substantially in the liquid phase, at a temperature in the range of about 160° C. to about 190° C. and for a time in a range of about 30 minutes to about 5 hours; and said contacting of (b)   is carried out at a pressure suitable to keep said organic amide substantially in the liquid phase, at a temperature of about 180° C. to about 210° C. and for a time in a range of about 30 minutes to about 8 hours.   
     
     
       18. A process for producing branched polyarylene sulfide sulfone, said process comprising: (a) contacting bis (p-chlorophenyl) sulfone monomer with phloroglucinol, N-methyl-2-pyrrolidone and sodium carbonate at a temperature of about 175° C. for about 1 to about 3 hours to produce a first reaction product mixture;   (b) contacting a reaction mixture comprising: (1) said first reaction product mixture,   (2) sodium hydrosulfide,   (3) N-methyl-2-pyrrolidone,   (4) sodium acetate, and   (5) water     at a temperature of about 200° C. for about 3 hours to produce polyarylene sulfide sulfone, and   (c) recovering said polyarylene sulfide sulfone from said reaction mixture.   
     
     
       19. A process of claim 1 wherein the mole ratio of organic amide to water is within the range of about 0.4:1 to about 1.3:1. the mole ratio of dihalo aromatic sulfone to polymerizable sulfur source is within the range of about 0.9:1 to about 2:1, the mole ratio of alkali metal carboxylate to polymerizable sulfur source is within the range of about 0.05:1 to about 4:1, the mole ratio of organic amide to polymerizable sulfur source is within the range of about 2:1 to about 24:1, the mole ratio of alkali metal carbonate to polymerizable sulfur source is within the range of about 1:1 to about 3:1, and the mole ratio of polyhydroxy aromatic compound to polymerizable sulfur source is within the range of about 1:1 to about 2:1. 
     
     
       20. A process of claim 19 wherein the mole ratio of organic amide to water is within the range of about 0.5:1 to about 1:1, the mole ratio of dihalo aromatic sulfone to polymerizable sulfur source ranges from about 0.95:1 to about 1.2:1, the mole ratio of alkali metal carboxylate to polymerizable sulfur source ranges from about 0.1:1 to about 2:1, the mole ratio of organic amide to polymerizable sulfur source is within the range of about 4:1 to about 16:1, the mole ratio of alkali metal carbonate to polymerizable sulfur source is within the range of about 1.5:1 to about 2.5:1, and the mole ratio of polyhydroxy aromatic compound to polymerizable sulfur source is within the range of about 1.25:1 to about 1.75:1. 
     
     
       21. A branched polyarylene sulfide sulfone made by the process of claim 1. 
     
     
       22. A branched polyarylene sulfide sulfone made by the process of claim 18.